Non-stick coating and method of forming same

ABSTRACT

Non-stick coatings for use on a flexible substrate include a fluoropolymer, an acrylic polymer, and a polyol and/or diol. The ratio of acrylic polymer to polyol and/or diol is between about 90:10 and about 10:90 by weight, preferably about 50:50. The ratio of acrylic polymer and polyol or diol to fluoropolymer is preferably about 100:60 by weight.

CROSS-REFERENCE TO RELATED PATENTS

This is a divisional of application Ser. No. 10/727,791, filed Dec. 3,2003, which is a continuing application of Ser. Nos. 60/430,455 and60/470,227.

BACKGROUND OF THE INVENTION

It is sometimes desirable to coat a flexible surface with a non-stickcoating. Traditional coatings that are used on rigid surfaces (e.g.cookware) are unacceptable because they are unable to bend and flexalong with the flexible surface. A specific application in which thisproblem has arisen concerns pressure rollers for printing machines.

Modern printing machines generally contain a heated fuser roller and anopposing pressure roller. As paper is fed between the rollers, theheated fuser roller melts (i.e., fuses) toner onto the paper to form thedesired image. The pressure roller applies sufficient pressure to thepaper to allow it to touch the fuser roller and have the image appliedto it. The pressure roller typically consists of a steel or aluminumcore that is coated with some type of rubber. The rubber on the pressureroller is flexible so that it can bend and adapt to the topographicalfeatures of the fuser roller and paper. The higher the quality of theimage desired, and the faster the printing rate of the printer orcopier, the softer the rubber on the pressure roller must be so that theink does not smudge when it melts. The rubber in modern high quality,high speed printers is commonly a very low durometer silicone rubber. Insome copiers, a single roller is capable of acting as the fuser roller,the pressure roller, or both. In addition, some printers apply siliconeoil to the roller in order to aid the release of toner.

It is desirable to apply a non-stick coating to the pressure rollers toprotect the soft rubber from chemical and thermal degradations, as wellas to prevent the paper and ink from sticking to the roller. Applying anon-stick coating to such soft rubber, however, presents a number ofproblems. First, it is difficult for conventional non-stick coatings tostick to this very soft silicone rubber because the non-stick coatingmust be able to bend and flex with the silicone rubber that it coats. Ifthe non-stick coating is not sufficiently flexible, it will crack and/orpeel away from the pressure roller during use. This decreases the printquality of the resultant image. Second, conventional fluoropolymercoatings are relatively hard when compared to the soft silicone rubbersused on pressure rollers. As a result, the non-stick coatings increasethe effective durometer of the pressure roller and decrease theconformability of the roller. This is counterproductive to the goal of avery soft pressure roller that produces a high quality image. Lastly, inthose situations where silicone oil is used, the silicone oil can attackthe silicone rubber and cause it to swell. Swelling of the siliconerubber is undesirable because it compromises the quality of the imageand the life of the roller.

Prior attempts at a non-stick coating for a pressure roller include theapplication of a fluoropolymer sleeve over the roller surface. Problemswith prior art fluoropolymer sleeves, however, include an unacceptableincrease in the effective durometer of the pressure roller and a highrate of delaminating due to shear stresses between the fluoropolymersleeve and the rubber roller. When a sleeve wears out (i.e.,delaminates), it peels away from the pressure roller and becomeswrinkled. The wrinkled pressure roller creates very poor quality imagesand must be replaced at great expense. For this reason, there is a needfor non-stick coating that can be used on a flexible surface, yet isdurable, functional, and low-cost.

BRIEF SUMMARY

A non-stick coating formulation is provided. The coating formulationcomprises an acrylic polymer, a polyol or a diol, and a fluoropolymer.The ratio of acrylic polymer to polyol is between about 90:10 and about10:90 by weight.

DETAILED DESCRIPTION

The non-stick coating of the present invention may be used to coat asubstrate of any desired hardness. The type of substrate to which thecoating is applied does not limit the scope of the invention. Thecoating of the present invention may be used on rigid surfaces (e.g.,cookware), though it is preferably used to coat a flexible surface. A“flexible surface” is any surface that deforms, bends, flexes, orchanges shape when subjected to an external force or pressure. In oneembodiment, the non-stick coating of the present invention is used tocoat a soft rubber pressure roller for use in a printing machine, suchas a high-speed digital copier or printer. Non-limiting examples of thesoft rubbers that may be coated with the non-stick coating of thepresent invention are silicone rubber, EPDM rubber (ethylene propylenerubber), and neoprene.

The non-stick coatings of the present invention may be applied to asubstrate in a one-coat process or a multi-coat process. An example of amulti-coat process is a two-coat process consisting of a primer coat anda top coat. The two-coat process results in a coating that is moredurable and has better release properties than the one-coat process,however, it may be more expensive.

The non-stick coatings of the present invention contain an acrylicpolymer and a diol or a polyol, or mixtures thereof. The ratio ofacrylic polymer to diol or polyol is preferably between 90:10 and 10:90by weight. Generally, the greater the ratio of acrylic polymer to diolor polyol, the stronger but less flexible the resultant coating will be.The preferred ratio of acrylic polymer to diol or polyol thereforedepends on the durometer of the substrate being coated and the desiredstrength of the coating. For example, a ratio of acrylic polymer to diolor polyol of 15:85 or lower is appropriate for a substrate having adurometer less than 10. (Unless otherwise stated, all references todurometer are based on the Shore A scale). For a substrate having adurometer greater than 10, a 50:50 or greater ratio may be used.

Useful acrylic polymers include polymers and copolymers of esters ofacrylic acid and methacrylic acid, such as methyl acrylate, methylmethacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate,propyl methacrylate, butyl acrylate, butyl methacrylate, and similarmonomers. The preferred acrylic polymer is hydroxy-functional. Preferredacrylic polymers are commercially available as an emulsion from S.C.Johnson & Son under the tradename JONCRYL 1540 or as a colloidaldispersion from Noveon Inc. under the tradename CARBOSET 514H. One ormore different acrylic polymers may be combined for use in the coatingformulations of the present invention. For example, a blend of JONCRYL1540 and CARBOSET 514H may be used. Such blends are useful to optimizeparticular characteristics of the coating, such as gloss and chemicalresistance.

The coatings of the present invention include a diol, a polyol, ormixtures thereof. As used herein, a diol is any alcohol that containstwo hydroxyl groups per molecule and a polyol is any alcohol thatcontains three or more hydroxyl groups per molecule. Useful diolsinclude urethanes, polyesters, acrylics or hybrid acrylic urethanes. Apreferred diol is a polyester diol commercially available from KingIndustries under the trade name K-FLEX XM 7304. Useful polyols includeurethanes, polyesters, acrylics or hybrid acrylic urethanes. A preferredpolyol is a polyurethane polyol commercially available from KingIndustries under the trade name K-FLEX XM 6304.

Preferably, a melamine is used to cross-link the acrylic polymer withthe diol or polyol. A preferred melamine is a methylated melamineformaldehyde resin and is commercially available from Cytec Industriesunder the tradenames CYMEL 325 or CYMEL 303. Another preferredmethylated melamine, hexamethoxymethyl melamine, is commerciallyavailable from UCB Inc. under the tradename RESIMENE 745. Desirably, thecross-linking is catalyzed with a blocked acid catalyst. A preferredcatalyst is a strong acid catalyst, para-toluene sulfonic acid (P-TSA),commercially available from King Industries under the tradename K-CURE1040W.

The non-stick coating of the present invention also includes afluoropolymer. The fluoropolymer is responsible for the non-stickquality of the coating. There are myriad commercially availablefluoropolymers and the specific fluoropolymer chosen does not limit thescope of the present invention. The fluoropolymer component of thepresent invention may include a single type of fluoropolymer, or mayinclude a mixture or blend of more than one type of fluoropolymer. Theratio of acrylic polymer and polyol or diol to fluoropolymer (i.e.,(acrylic polymer+polyol/diol):fluoropolymer) is preferably about 100:60in the formulation for a one-coat system and between about 90:10 andabout 70:30 for a formulation intended to be applied as an intermediatecoat. Depending on the particular application, it is desirable for theratio of acrylic polymer and polyol or diol to fluoropolymer in the topcoat to be between about 70:30 and about 30:70. A roller that is to beused in a copier that does not use silicone oil preferably includes atop coat having a ratio of acrylic polymer and polyol or diol tofluoropolymer of about 30:70.

Exemplary fluoropolymers are tetrafluoroethylene-perfluoromethyl vinylether copolymer (MFA), tetrafluoroethylene-hexafluoropropylene copolymer(FEP), and polytetrafluoroethylene (PTFE). FEP is a preferredfluoropolymer. The preferred FEP is commercially available as awater-based latex dispersion commercially available from Dyneon LLC andsold under the trade name DYNEON FEP X 6300. PTFE is another preferredfluoropolymer. The preferred PTFE is commercially available as amicropowder from Asahi Chemical and sold under the trade name WITCONTL-10.

Non-limiting examples of other acceptable fluoropolymers arepolychloro-trifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylenecopolymer (ECTFE), ethylene-tetrafluoroethylene copolymer (ETFE),tetrafluoroethylene (TFE) and perfluoro (ethyl vinyl ether) (PEVE)copolymer (PFA), TFE and perfluoro (propyl vinyl ether) (PPVE) copolymer(PFA), polyvinylfluoride (PVF), and polyvinylidene fluoride (PVDF). Thefluoropolymer component may also include comonomer modifiers thatimprove selected characteristics.

The fluoropolymer may be a micropowder. Alternatively, the fluoropolymermay be provided in the form of a dispersion of fluoropolymer in water.By “dispersion” it is meant that the fluoropolymer particles are stablydispersed in water so that the particles do not settle before thedispersion is used. In some cases it may be desirable to include anorganic solvent, such as n-methylpyrrolidone, butyrolactone, highboiling aromatic solvents, alcohols, or mixtures thereof.

The coating system of the present invention may include a silane. Thesilane may be included as an ingredient in a formulation for a one-coatsystem or applied as the first coat in a multi-coat system. Preferredsilanes include vinyltrimethoxysilane,gamma-methacycloxypropyltrimethoxy silane, vinyltris (t-butylperoxy)silane and partially hydrolyzed silanes. The preferred silane for use ina one coat formulation is commercially available from Dowcon under thetradename Z-6020. The silane preferably comprises between 1.0 and 2.5%by weight of the total non-stick coating formulation. For a multi-coatsystem, the preferred silane is commercially available from Shin-EtsuChemical Co. under the tradename X33-156-5. Alternatively, a one-coatformulation containing a silane may be applied as the primer (or otherlayer) in a multi-coat system.

The coating system of the present invention may include an additive toaid release. The preferred release additive is a polyether modifieddimethylpolysiloxane copolymer in a butylglycol solvent that iscommercially available from BYK-Chemie GmbH under the tradename BYK-301.

The coating system of the present invention may include a dispersant.The preferred dispersant is an acetylene diol dispersant that iscommercially available from Air Products and Chemicals, Inc. under thetradenames SURFYNOL CT 324 or SURFYNOL 104BC.

Following is a specific example of a one-coat formulation. Thecomposition comprises 29.9% acrylic emulsion (43% in water), 2.7% PTFEmicropowder, 4.5% propylene glycol, 8.3% propylene glycol, 2.7% alkylphenol polyethelyeneoxide, 13.2% polyester diol (30% emulsion in water),0.3% blocked acid catalyst, 0.9% silane, 0.5% acetylene diol dispersant,and 9.3% methylated melamine formaldehyde resin. The balance of theformulation is water and additives. Each additive comprises less than 2%of the composition. The additives include well known defoamers, flowagents, dispersants, surfactants, stabilizers, thickeners and/orfillers.

The one-coat formulation is filtered through a mesh filter rated at 53microns and sprayed onto the substrate by conventional or high volume,low pressure (HVLP) methods. The thickness of the dry coat is from about20 to about 30 microns.

The coating is cured for about ten minutes in a conventional ovenoperating at approximate 450° F. The silicone rubber that is commonlyused to coat pressure rollers begins to thermally decompose at about500-550° F. Thus, it is desirable to cure the coating in such a mannerthat the temperature of the silicone rubber stays below 500° F.

As noted above, the non-stick coating of the present invention can beapplied in a two-coat process. The first coat is a primer that helpsbond a subsequent layer which contains a fluoropolymer to the substrate.Any primer that effectively bonds to the chosen substrate is acceptable.Where the substrate consists of silicone rubber or other rubber having ahydroxy functional group (such as EPDM rubber), the primer is preferablya silane primer as described above. The primer component may consist ofa single type of primer; alternatively, different primers may be mixedor combined to form the primer. The primer is preferably applied as avery thin layer having a thickness of between one molecule to a fewmicrons. The primer may be applied by wiping it on the substrate with acloth or by conventional or HVLP spray guns. The applied primer istypically very volatile and may be dried by any desirable means, thoughit is preferably dried in a conventional oven at 150° F. for about 3-5minutes or at air temperature (−77° F.) for about fifteen minutes.

A first embodiment of a top coat composition comprises 23.0% acrylicpolymer emulsion (43% in water), 13.1% PTFE micropowder, 6.5% propyleneglycol, 8.3% propylene glycol, 2.1% alkyl phenol polyethelyeneoxide,10.2% polyurethane diol (30% emulsion in water), 1% silane, 0.5%acetylene diol dispersant, and 0.3% blocked acid catalyst. The balanceof the formulation is water and additives. Each additive comprises lessthan 2% of the composition. The additives include well known defoamers,flow agents, dispersants, surfactants, stabilizers, thickeners and/orfillers. This composition has a ratio of acrylic polymer to diol ofabout 85:15 and a ratio of acrylic polymer and polyol to fluoropolymerof about 70:30.

A second embodiment of a top coat composition comprises approximately 7%acrylic polymer emulsion, 22% polyurethane polyol, 7.1% methylatedmelamine formaldehyde resin, 17.8% FEP dispersion, 0.3% blocked acidcatalyst, 6.7% propylene glycol, and 5% of a polyether modifieddimethylpolysiloxane copolymer release agent. The balance of theformulation is water and additives. Each additive comprises less than 2%of the composition. The additives include well known defoamers, flowagents, dispersants, surfactants, stabilizers, thickeners and/orfillers. This composition has a ratio of acrylic to polyol of about85:15 and a ratio of acrylic polymer and polyol to fluoropolymer ofabout 70:30. This embodiment of a top coat is particularly useful wherethe coated roller may come in contact with silicone oil.

The preferred thickness of the top coat varies according to the hardnessof the substrate. If the durometer of the substrate is less than 10, thethickness of the top coat is preferably less than 5 microns. If thedurometer of the substrate is between 10 and 20, the thickness of thetop coat is preferably less than 7 microns. If the durometer of thesubstrate is greater than 20, the thickness of the top coat ispreferably greater than 10 microns, most preferably about 20-30 microns.The top coat is sprayed directly on top of the dried primer and thearticle is cured in a conventional oven at about 400° F. for about 10minutes. If the coating is to be used in a copier that uses siliconeoil, it is desirable to cure the coating at a lower temperature, e.g.,about 350° F. The lower temperature is preferred in order to avoid theformation of a completely melted, continuous network of fluoropolymer. Adiscontinuous network of fluoropolymer is preferred because it createsinterstices that absorb silicone oil and aid efficient operation of thecopier.

In another embodiment, the non-stick coating of the present inventioncan be applied in a three-step process. The first coat is a primer thathelps bond a subsequent layer which contains a fluoropolymer to thesubstrate. Any primer that effectively bonds to the chosen substrate isacceptable. Where the substrate consists of silicone rubber or otherrubber having a hydroxy functional group (such as EPDM rubber), theprimer is preferably a silane primer as described above. The primercomponent may consist of a single type of primer; alternatively,different primers may be mixed or combined to form the primer. Theprimer is preferably applied as a very thin layer having a thickness ofbetween one molecule to a few microns. The primer may be applied bywiping it on the substrate with a cloth or by conventional or HVLP sprayguns. The applied primer is typically very volatile and may be dried byany desirable means, though it is preferably dried in a conventionaloven at 150° F. for about 3-5 minutes or at air temperature (−77° F.)for about fifteen minutes.

The first embodiment of a top coat described above with respect to thetwo-coat process is an acceptable mid-coat for the three-coat process.Another embodiment of a mid-coat composition comprises approximately 7%acrylic polymer emulsion, 22% polyurethane polyol, 7.1% methylatedmelamine formaldehyde resin, 17.8% FEP dispersion, 0.5% acetylene dioldispersant, 0.3% blocked acid catalyst, and 6.7% propylene glycol. Thebalance of the formulation is water and additives. Each additivecomprises less than 2% of the composition. The additives include wellknown defoamers, flow agents, dispersants, surfactants, stabilizers,thickeners and/or fillers. This composition has a ratio of acrylic topolyol of about 85:15 and a ratio of acrylic and polyol to fluoropolymerof about 70:30.

A preferred top coat for the three-coat process further includes arelease additive and a higher percentage of fluoropolymer. The preferredtop coat composition comprises approximately 4.1% acrylic polymeremulsion, 12.3% polyurethane polyol, 3.8% polypropylene glycol, 3.9%methylated melamine formaldehyde resin, 53.9% FEP dispersion, and 5.7%of a release additive, such as a polyether modified dimethylpolysiloxanecopolymer. The composition has a ratio of acrylic polymer to diol ofabout 85:15 and a ratio of acrylic polymer and polyol to fluoropolymerof about 30:70.

The three-coat system described above is cured at about 550° F. forabout 10 minutes. It is desirable to cure the system at a sufficienttemperature, and for a sufficient time, to melt the fluoropolymer into acontinuous network.

Any of the coatings described herein can be made to be conductive. Inhigh-speed copiers it is very easy for a large static charge to build upin the paper and to compromise image quality. For this reason, it may bedesirable to have a conductive coating that dissipates the staticcharge. The coatings discussed above may be made conductive by theaddition of an electrically conductive pigment such as KETJEN BLACK,which is commercially available from Akzo-Nobel Coating Inc.

Specific one-coat and two-coat embodiments are provided above, however,the number of coats employed does not limit the scope of the presentinvention. Non-stick coatings of the present invention may also consistof three or more coats. For example, it may be desirable to use twodifferent primers or it may be desirable to add one or more intermediatecoats.

While particular embodiments of the present invention have beenillustrated and described above, the present invention should not belimited to such examples and descriptions. It should be apparent thatchanges and modifications may be incorporated and embodied as part ofthe present invention within the scope of the following claims.

1. A non-stick coating formulation comprising: a. an acrylic polymer, b.an alcohol selected from the group consisting of a diol, a polyol, andmixtures thereof, and c. a fluoropolymer, and d. a cross-linking agentfor cross-linking the acrylic polymer with the alcohol.
 2. The non-stickcoating formulation of claim 1, further comprising a silane.
 3. Thenon-stick coating formulation of claim 1, wherein the ratio of acrylicpolymer to the alcohol is between about 90:10 and about 10:90 by weight.4. The non-stick coating formulation of claim 1, wherein thecross-linking agent is a melamine.
 5. The non-stick coating formulationof claim 1, wherein the cross-linking agent is a methylated melamineformaldehyde.
 6. The non-stick coating formulation of claim 1, whereinthe alcohol comprises a polyester diol.
 7. The non-stick coatingformulation of claim 1, wherein the alcohol comprises a polyurethanepolyol.
 8. The non-stick coating formulation of claim 1, furthercomprising a polyether modified dimethylpolysiloxane copolymer.
 9. Thenon-stick coating formulation of claim 1, further comprising a blockedacid catalyst.
 10. A coated substrate comprising: a. a substrate, and b.a non-stick coating, wherein the non-stick coating comprises: i. anacrylic polymer cross-linked with an alcohol selected from the groupconsisting of a diol, a polyol, and mixtures thereof; and ii. afluoropolymer.
 11. The coated substrate of claim 10, wherein the acrylicpolymer and the alcohol are cross-linked with a melamine.
 12. The coatedsubstrate of claim 10, wherein the acrylic polymer and the alcohol arecross-linked with a methylated melamine formaldehyde in the presence ofa blocked acid catalyst.
 13. The coated substrate of claim 10, whereinthe ratio of acrylic polymer to the alcohol is between about 90:10 andabout 10:90 by weight.
 14. The coated substrate of claim 10, furthercomprising a silane.
 15. The coated substrate of claim 10, wherein thealcohol comprises a polyester diol.
 16. The coated substrate of claim10, wherein the alcohol comprises a polyurethane polyol.
 17. The coatedsubstrate of claim 10, further comprising a polyether modifieddimethylpolysiloxane copolymer.
 18. The coated substrate of claim 10,wherein the rubber comprises silicone rubber.
 19. The coated substrateof claim 11, wherein the rubber comprises silicone rubber.
 20. Thecoated substrate of claim 10, wherein the durometer of the rubber isless than about 10.